EP0494936B1 - Gels - Google Patents

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Publication number
EP0494936B1
EP0494936B1 EP90915161A EP90915161A EP0494936B1 EP 0494936 B1 EP0494936 B1 EP 0494936B1 EP 90915161 A EP90915161 A EP 90915161A EP 90915161 A EP90915161 A EP 90915161A EP 0494936 B1 EP0494936 B1 EP 0494936B1
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Prior art keywords
composition according
additive
phosphate
composition
weight
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EP90915161A
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German (de)
English (en)
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EP0494936A1 (fr
Inventor
Alistair Alfred Preston Sutherland
John Michael 158 Oxford Road Hudson
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Raychem Ltd
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Raychem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers

Definitions

  • This invention relates to a gel composition, by which is meant a liquid-extended polymer composition having a cone penetration value (measured by a modified version of ASTM D217, as described below) within the range from 50 to 400 (10 ⁇ 1 millimetres); and preferably an ultimate elongation (measured by ASTM D412 as described below) greater than 100%, with substantially elastic deformation to an elongation of at least 100%; ultimate tensile strength (ASTM D412) less than 1 MegaPascal; and dynamic storage modulus (as hereinafter described) less than 100000 Pascals.
  • the composition may either contain a three-dimensional network of cross-linked molecular chains (gels) or may merely behave as if it contained such a network (gelloids).
  • Oil-extended compositions of block copolymers are known, for example from US-A-3676387 (Lindlof), US-A-3827999 (Crossland), US-A-4176240 (Sabia), and US-A-4369284 (Chen), and published International Patent Application WO-A-8800603, and it has previously been found necessary to subject copolymer-oil adhesive compositions to radiation cross-linking in order to modify their physical and adhesive properties, as described for example in European Published Patent Application EP-A-0224389 (Raychem, Gamarra), US-A-4151057 (St Clair) and in "Radiation Curing of PSA's Based on Thermoplastic Rubbers" by D.J. St. Clair, in Adhesives Age, March 1980, pages 30-36.
  • the present invention improves the characteristics of gel or gelloid compositions (hereinafter referred to simply as "gels") without the problem of crosslinking.
  • the present invention is capable of alleviating this problem, and in some cases may furthermore improve the properties of the gel.
  • the invention accordingly provides a gel or gelloid liquid-extended polymer composition having (i) an ASTM D217 cone penetration value within the range from 50 to 400 (10 ⁇ 1 millimetres), (ii) an ASTM D412 ultimate elongation greater than 100% with substantially elastic deformation to an elongation of at least 100%, (iii) an ASTM D412 ultimate tensile strength of less than 1 MegaPascal, and (iv) a dynamic storage modulus at 23°C of less than 100000 Pascals; the composition comprising an intimate mixture of
  • Ts A "significant" depression of the softening point (hereinafter Ts) may be regarded as more than about 5°C for example, although this working guideline may vary in accordance with circumstances, such as the range of temperatures over which the gel is intended to operate.
  • the invention is particularly concerned with gel or gelloid compositions in which the gel-forming polymer mainly (more than 50%, preferably more than 90%, especially 95-100%, of the total polymer) comprises the block copolymer materials having relatively hard blocks and relatively elastomeric blocks (e.g. hydrogenated rubber blocks).
  • the block copolymer materials having relatively hard blocks and relatively elastomeric blocks (e.g. hydrogenated rubber blocks).
  • Especially interesting block copolymers for the purposes of this invention are those wherein the hard blocks comprise polystyrene.
  • the weight ratio of the hard blocks to the elastomeric blocks in those (and other) copolymers is preferably within the range from 0.25:1 to 0.75:1.
  • the elastomeric blocks preferably comprise a polyalkylene material, preferably a hydrogenated rubber.
  • styrene-alkylene block copolymers examples include styrene-alkylene-styrene triblock copolymers such as styrene-diene tri-block copolymers (linear or radial), for example styrene-butadiene-styrene or styrene-isoprene-styrene or styrene-(ethylene-butylene)-styrene triblock copolymers.
  • styrene-alkylene-styrene triblock copolymers such as styrene-diene tri-block copolymers (linear or radial), for example styrene-butadiene-styrene or styrene-isoprene-styrene or styrene-(ethylene-butylene)-styrene triblock copolymers.
  • block copolymers useful in the present invention are the hydrogentated styrene-diene block copolymers in which the styrene blocks have a molecular weight within the range from 2000 to 50000 and the diene blocks have a molecular weight within the range from 20000 to 300000.
  • Preferred are those having at least two styrene end-blocks and at least one diene mid-block, the styrene end blocks comprising up to 55% by weight of the block copolymer.
  • examples include poly(styrene-ethylene-butylene-styrene) triblock copolymers generally referred to as SEBS triblock copolymers.
  • copolymers have styrene end blocks and ethylene and butylene centre blocks and are characterised by the ratio of styrene blocks to the combined ethylene-butylene blocks.
  • Blends of two different SEBS triblock copolymers e.g. as described in European Published Patent Application EP-A-0224389 (Gamarra), can be used to provide oil-extended elastomeric gels according to this invention having certain desired cone penetration, elongation and tensile strength properties.
  • styrene-diene block copolymers useful in compositions of this invention include poly(styrene-butadiene-styrene) block copolymers (SBS), poly(styreneisoprene-styrene) block copolymers (SIS) and similar known styrene-diene block copolymers.
  • SBS poly(styrene-butadiene-styrene) block copolymers
  • SIS poly(styreneisoprene-styrene) block copolymers
  • the SEBS block copolymers are preferred.
  • the copolymer material (a) may comprise mixtures of two or more block copolymers.
  • PPO polyphenylene ethers
  • poly(2,6-dimethyl-1,4-phenylene)ether poly(2,6-dimethyl-1,4-phenylene)ether
  • At least one (preferably all) material of the additive (c), and preferably also of the extender liquid (b), is (are) substantially incompatible with the copolymer hard blocks.
  • At least one of the materials (i) and (ii) of the non-polymeric additive has a solubility parameter (calculated from Small's group molar attraction constants) of at least 37.67 (9), preferably within the range from 37.67 to 44.37 (9.0 to 10.6), more preferably 40.10 to 44.16 (9.58 to 10.55), and especially 41.86 to 44.04 (10.00 to 10.52) [J/cm3]0 ⁇ 5 (cal/cm3]0 ⁇ 5).
  • solubility parameter calculated from Small's group molar attraction constants
  • Ts gel softening temperature
  • materials 1 to 10 with the exception of material 8, severely depressed Ts. Many of these materials are known as PVC plasticisers, and so may have a useful equilibrium-forming stabilising effect when used as material (i) of additives according to this invention, together with a temperature-raising material (ii). Materials 8 and 11 to 16 were all found, in separate tests, to have a stabilising effect due to their resistance to migration of PVC plasticisers into the gel (hereinafter "plasticiser resistance”) and could accordingly be used alone as the stabilising material (i) of the additive.
  • plasticiser resistance a stabilising effect due to their resistance to migration of PVC plasticisers into the gel
  • Materials 8 and 11 had only an insignificant effect on Ts, whereas materials 12 to 16 significantly raised Ts and could thus also be used as material (ii) of the additive together with stabilising materials (i) for example equilibrium-forming plasticisers such as materials 1 to 7, 9 and 10.
  • stabilising materials for example equilibrium-forming plasticisers such as materials 1 to 7, 9 and 10.
  • Such material (ii) could compensate for the depression of Ts caused by the stabilisers (i) or could raise Ts in cases where it is unaffected by the stabilisers.
  • material 14 could be used to counteract the depressive effect of material 4.
  • Materials 17 and 18 do not significantly depress Ts, but were found on testing to lack stabilising effect, and are thus of no interest for the present invention.
  • Materials 19 to 24 all raise Ts (No.23 barely significantly), but also lack stabilising effect. Materials 19 to 24 could therefore be used as the temperature-raising material (ii) of the additive together with suitable stabilising materials (i) to compensate for depression of Ts, or to raise Ts, as aforesaid.
  • suitable stabilising materials i
  • At least one (preferably both) of the materials (i) and (ii) (when present) of the additive is (are) liquid at room temperature and miscible with the extender liquid (b).
  • solid materials such as materials 19 to 24 may still be useful for some purposes, especially if they have good solubility in the extender liquid.
  • Plasticiser-stabilising effect can be tested, for example, by encapsulating weighed plasticised PVC samples in a gel containing the additive to be tested, for example in the aforementioned proportions, and maintaining the encapsulated samples at 70°C for suitable periods, e.g. a week or a fortnight or two. After removal from the gel, which usually peels cleanly from the sample surface, the samples are re-weighed, and any loss of weight may be compared with that of the control to see if the additive reduces the degree of loss of the PVC plasticiser into the gel.
  • the additive materials having solubility parameter (S.P.) greater than 9 will not only preferably be liquids as aforesaid but will also preferably exclude oxygen-heterocyclic aromatics (material 9); alkanols; and glycols and polyols and their mono-ethers and mono-esters (e.g. materials 10, 17, 18).
  • Materials of S.P. below 9 tend to depress Ts (e.g. materials 1 to 7, 9, 10), while materials of S.P. above 10.6 may tend to have problems as indicated above for materials 17 to 24.
  • S.P. of 9.58 to 10.55 excludes the short chain alkyl phosphate material 8, while the range of S.P.
  • from 10.00 to 10.52 includes the most beneficial materials 12 to 16, most of which are organic phosphates, as is preferred.
  • Halogenated (preferably chlorinated) or unhalogenated phosphates e.g. alkyl phosphates having up to 6, preferably up to 4 carbon atoms in each alkyl group, and aryl phosphates, are especially preferred.
  • Materials containing polar carbonyl or sulpho groups may also be desirable for raising Ts, in view of the results achieved by materials 13 and 19 to 24.
  • Mixtures of materials (i) and mixtures of materials (ii) may be used if desired.
  • cross-linking of the composition may still be effected if desired, and may produce further improvements in properties.
  • Mixtures comprising less than 300 parts, especially 200 parts or less, of the extender liquid, e.g. as in the hot melt adhesives described in US-A-4141876 and US-A-4104323, per 100 parts of block copolymer, generally do not behave as gel or gelloid compositions. Such mixtures tend to be too hard and to have too high an ultimate tensile strength and dynamic storage modulus, especially when tackifying resins are added.
  • Preferred gel or gelloid compositions according to the present invention either have a cone penetration value within the range from 200 to 400 (10 ⁇ 1 millimetres) ("soft gels"), and comprise preferably at least 567, and preferably not more than 5000 parts by weight of the extender liquid per 100 parts by weight of the polymer; or have a cone penetration value within the range from 50 to 199 (10 ⁇ 1 millimetres) ("hard” gels), and comprise preferably 300-566 parts by weight of the extender liquid per 100 parts of the polymer.
  • soft gels preferably at least 567, and preferably not more than 5000 parts by weight of the extender liquid per 100 parts by weight of the polymer
  • hard gels preferably 300-566 parts by weight of the extender liquid per 100 parts of the polymer.
  • the extender liquid preferably has a boiling point higher than the softening or melting temperature of the gel copolymer, and the extender liquid is preferably mixed with the copolymer at a temperature not less than its melting or softening temperature. Mastication or other mixing techniques at lower temperatures, perhaps with the aid of volatile solvents, may however be used if the resulting composition is acceptable for the intended end use.
  • the extender liquids useful in the compositions of this invention comprising the block copolymer and plasticiser-stabilising additive as aforesaid may be selected from oils conventionally used to extend elastomeric materials.
  • the oil may be a hydrocarbon oil such as paraffinic or naphthenic oils, synthetic oils such as polybutene or polypropene oils, and mixtures thereof.
  • the preferred oils are substantially non-aromatic mixtures of paraffins and naphthenic hydrocarbon oils.
  • the oils should have a minimum boiling point higher than the softening point of the block copolymer(s).
  • suitable oils include those available from Fina Chemicals under the Trade Mark “Fina Vestan” in grade A360B (preferred), under TM “Drakeol 34" from Penreco, and under TM “Witco 380PO” from Witco.
  • the ratio of polymer to the oil will generally range from 2 to 30 parts polymer mixture to 70 to 98 parts oil. In general, for "soft" gels, it is preferred to use 3 to 15 parts of the block copolymer with 97 to 85 parts oil and most preferred for many application to use from 4 to 12 parts of the copolymer, with 96 to 88 parts oil. For “hard” gels, a ratio of 15 to 30 parts of the block copolymer, most preferably from 18 to 25 parts, with the balance oil, is preferred.
  • compositions of this invention are preferably prepared by mixing the oil with a blend of the polymer(s) and the additive material(s) at a temperature not less than the glass transition temperature of the hard blocks in the said block copolymer.
  • the glass transition temperature of the hard blocks may have been raised by blending with PPO as described in the aforementioned WO-A-8800603).
  • sufficiently high temperatures and sufficient mixing shear are preferably used.
  • the mixing at the elevated temperature should be continued until the mixture is uniform and all of the polymers are evenly dispersed or blended in the oil.
  • the composition is then moulded into the desired shapes and allowed to cool.
  • the resulting elastomeric composition can be re-melted and again cooled without any significant change in physical properties.
  • oils useful in the radiation-cross-linked versions of the compositions of this invention can, for example, be the same oils as above.
  • the cross-linking agents useful in the electron beam radiation cross-linking of the polymer-oil composition, the amount of cross-linking agent, and the electron beam radiation dosage will depend on the composition, its configuration and the degree of cross-linking desired, and may be selected by the usual criteria, for example along the lines disclosed in the aforementioned European Published Patent Application EP-A-0224389.
  • additives for various purposes in any of the compositions of this invention.
  • Such additives may be stabilisers, antioxidants, flame retardants, tackifiers, or corrosion inhibitors. It is useful to use antioxidants in all the compositions of this invention.
  • compositions of this invention can be made having a wide range of physical properties, such as cone penetration, ultimate elongation, and tear strength, desirable for particular end use applications.
  • the compositions have numerous uses as elastomeric materials and in particular may be used as sealing materials, for example as illustrated in European Published Patent Applications EP-A-0108518 and EP-A-0191609, although the compositions of this invention will have many and varied uses depending on the properties desired and the temperatures to be encountered.
  • Gel compositions within the scope of this invention are preferably defined by the following criteria (1) to (8), of which preferably not more than one criterion (not (1) or (2)) will be outside the specified ranges. These criteria are derived from Tests I to V described in the aforementioned WO-A-8800603.
  • the softening point (Ts) of the gel compositions increases as the proportion of temperature - raising additive increases.
  • the amount of additive is at least 3%, preferably at least 5%, and not more than 25% by weight of the whole gel composition, more preferably 10 to 15 weight per cent.
  • Softening point of the gel compositions is determined by standard Thermal Mechanical Analysis Techniques, such as the duPont TMA using a load of 5 grammes and a heating rate of 5°C per minute.
  • the materials were stirred cold, under nitrogen, for at least 30 minutes in order to flush the flask of air and allow the copolymer to absorb some of the oil. Heat was applied steadily until considerable swelling occurred and the mixture became very viscous (depending on the plasticiser this could occur at any temperature in the range 80-180°C). Heat was then applied with caution and was maintained until a homogeneous, molten gel containing no undissolved copolymer was observed or up to a maximum temperature of 220°C. Heating and stirring were stopped and after the gel had become cold and set, the flask was uncovered and the gel removed intact.
  • the gels of this invention may be especially useful when used as a sealant in an electrical connection terminal enclosure, cable splice, or cable termination, or in a kit or component for making such an enclosure, splice, or termination.
  • the Ts of these gels was 128°C for example A and 124°C for the example B, compared with Ts of 125°C for the same gel replacing the Genemol and Bisoflex additives with a corresponding additional amount of the oil.
  • the gels preferably contain at least 75 parts by weight (more preferably at least 100 parts by weight, especially at least 150 parts by weight, and in some cases even 200 or more parts by weight) of the said additive per 100 parts by weight of the block copolymer material (a).
  • the gel composition may comprise 5 to 25, preferably 10 to 15, weight percent of the additive, based on the weight of the whole composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Connector Housings Or Holding Contact Members (AREA)

Abstract

Des gels de copolymères en bloc durs et à élastomère dur constitués d'au moins 300 parties de liquide diluant par 100 parties du copolymère, contiennent au moins 50 parties (par 100 parties de copolymère) d'un additif stabilisateur qui s'oppose à la migration des plastifiants de CVP vers le gel lorsque ce dernier se trouve en contact avec un article en CVP plastifié. On préfère des copolymères en bloc triple de styrène-(éthylène-butylène)-styrène à stabilisateurs phosphatés organiques, car ces stabilisateurs ont tendance à élever la température de ramollissement.

Claims (21)

  1. Composition de polymère étendue avec un liquide, du type gel ou gelloïde, ayant (1) une valeur de pénétration de cône suivant la norme ASTM D217 comprise dans l'intervalle de 50 à 400 (10⁻¹ mm), (ii) un allongement à la rupture ASTM D412 supérieur à 100 %, avec une déformation pratiquement élastique à un allongement d'au moins 100 %, (iii) une résistance à la rupture ASTM D412 inférieure à 1 mégapascal, et (iv) un module de stockage dynamique à 23°C inférieur à 100 000 pascals, la composition comprenant un mélange intime
    (a) d'au moins un copolymère séquencé contenant des blocs relativement durs et des blocs relativement élastomères ;
    (b) d'au moins 300 parties en poids d'un liquide d'extension pour 100 parties en poids du ou des copolymères, liquide qui étend et ramollit les blocs élastomères ; et
    (c) d'au moins 50 parties en poids, pour 100 parties en poids du ou des copolymères (a), d'un additif stabilisant le plastifiant comprenant
    (i) une matière stabilisante capable d'établir un équilibre quasi-total avec un ou plusieurs, ou de s'opposer à la migration dans la composition d'un ou plusieurs, plastifiants du PVC d'un article en PVC plastifié avec lequel la composition utilisée doit être placée en contact de surface,
    et la matière stabilisante (i) élève ou n'abaisse pas notablement la température de ramollissement de la composition, auquel cas l'additif (c) peut comprendre facultativement
    (ii) une matière élevant la température, qui élève la température de ramollissement de la composition,
    ou bien la matière stabilisante (i) abaisse notablement la température de ramollissement de la composition, auquel cas l'additif (c) comprend une quantité de la matière élevant la température (ii) suffisante pour compenser au moins 50 % de l'abaissement de température provoqué par la matière stabilisante.
  2. Composition suivant la revendication 1, dans laquelle les blocs durs du copolymère comprennent le polystyrène.
  3. Composition suivant la revendication 1 ou 2, dans laquelle les blocs élastomères du copolymère comprennent un polyalkylène.
  4. Composition suivant les revendications 2 et 3, dans laquelle le copolymère est un copolymère séquencé styrène-alkylène.
  5. Composition suivant l'une quelconque des revendications précédentes, dans laquelle toutes les substances de l'additif (c) et du liquide d'extension (b) sont pratiquement incompatibles avec les blocs durs du copolymère.
  6. Composition suivant l'une quelconque des revendications précédentes, dans laquelle au moins une des matières (i) et (ii) de l'additif a un paramètre de solubilité (calculé à partir des constantes d'attraction molaire des groupes de Small) d'au moins 37,67 [J/cm³]⁰ʼ⁵ (9) (cal/cm³)⁰ʼ⁵.
  7. Composition suivant la revendication 6, dans laquelle le paramètre de solubilité est compris dans l'intervalle de 37,67 (9,0) à 44,37 (10,6).
  8. Composition suivant la revendication 6 ou 7, dans laquelle au moins une des matières (i) et (ii) (lorsqu'elle est présente) de l'additif est liquide à température ambiante et miscible avec le liquide d'extension (b).
  9. Composition suivant l'une quelconque des revendications précédentes, dans laquelle la matière stabilisante (i) de l'additif est un plastifiant pour PVC et l'additif comprend la matière élevant la température (ii).
  10. Composition suivant la revendication 7, 8 ou 9, dans laquelle l'une des, mais non les deux, matières (i) et (ii) (si elles sont présentes) de l'additif consiste en dibenzoate de 2,2-oxybis(éthanol).
  11. Composition suivant la revendication 7, 8 ou 9, dans laquelle l'une des, mais non les deux, matières (i) et (ii) (si elles sont présentes) de l'additif est un phosphate organique.
  12. Composition suivant la revendication 11, dans laquelle le phosphate est un phosphate d'alkyle ayant jusqu'à 6 atomes de carbone dans chaque groupe alkyle.
  13. Composition suivant la revendication 11, dans laquelle le phosphate est un phosphate d'aryle.
  14. Composition suivant la revendication 11, 12 ou 13, dans laquelle le phosphate est un phosphate halogéné.
  15. Composition suivant la revendication 11, dans laquelle le phosphate est le phosphate de triphényle, le phosphate de tris(1-chroéthyle), le 2,2-bis (chlorométhyl)-1,3-propylène- (bis(2-chloréthyl)phosphate ou le phosphate de tris(1,3-dichloropropyle).
  16. Composition suivant la revendication 11, dans laquelle le phosphate est le phosphate de triéthyle ou le phosphate de tris(1-chloroprop-2-yle).
  17. Composition suivant l'une quelconque des revendications précédentes, comprenant 5 à 25 % en poids de l'additif, sur la base du poids de la composition totale.
  18. Composition suivant l'une quelconque des revendications 1 à 15, comprenant au moins 75 parties en poids de l'additif pour 100 parties en poids du copolymère séquencé (a).
  19. Composition suivant l'une quelconque des revendications 1 à 15, dont la température de ramollissement est supérieure à celle de la composition du type gel correspondante dépourvue de l'additif.
  20. Composition suivant l'une quelconque des revendications précédentes, lorsqu'elle est utilisée comme agent d'étanchéité dans un boîtier terminal de connexion électrique, une épissure ou une terminaison de câble, ou dans un kit ou un composant pour la production d'un tel boîtier, d'une telle épissure ou d'une telle terminaison.
  21. Composition suivant l'une quelconque des revendications précédentes, ayant une valeur de pénétration de cône ASTM D217 comprise dans l'intervalle (a) de 200 à 400 (10⁻¹ mm) ou (b) de 50 à 199 (10⁻¹mm).
EP90915161A 1989-10-05 1990-10-02 Gels Expired - Lifetime EP0494936B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB8922445 1989-10-05
GB898922445A GB8922445D0 (en) 1989-10-05 1989-10-05 Gels
PCT/GB1990/001505 WO1991005014A1 (fr) 1989-10-05 1990-10-02 Gels

Publications (2)

Publication Number Publication Date
EP0494936A1 EP0494936A1 (fr) 1992-07-22
EP0494936B1 true EP0494936B1 (fr) 1996-02-07

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EP (1) EP0494936B1 (fr)
JP (1) JP2971133B2 (fr)
KR (1) KR0149874B1 (fr)
AR (1) AR245509A1 (fr)
AT (1) ATE133987T1 (fr)
AU (1) AU638287B2 (fr)
BR (1) BR9007719A (fr)
CA (1) CA2065730C (fr)
DE (1) DE69025331T2 (fr)
GB (1) GB8922445D0 (fr)
WO (1) WO1991005014A1 (fr)

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CA2065730C (fr) 2002-01-01
DE69025331D1 (de) 1996-03-21
AR245509A1 (es) 1994-01-31
EP0494936A1 (fr) 1992-07-22
WO1991005014A1 (fr) 1991-04-18
ATE133987T1 (de) 1996-02-15
DE69025331T2 (de) 1996-10-10
GB8922445D0 (en) 1989-11-22
AU6508190A (en) 1991-04-28
AU638287B2 (en) 1993-06-24
CA2065730A1 (fr) 1991-04-06
KR0149874B1 (ko) 1999-05-15
JP2971133B2 (ja) 1999-11-02
JPH05500976A (ja) 1993-02-25
BR9007719A (pt) 1992-08-11
KR927003722A (ko) 1992-12-18

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